WO2009056109A1 - Procédé de production d'un composite stratifié à base de polycarbonate - Google Patents

Procédé de production d'un composite stratifié à base de polycarbonate Download PDF

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Publication number
WO2009056109A1
WO2009056109A1 PCT/DE2008/001750 DE2008001750W WO2009056109A1 WO 2009056109 A1 WO2009056109 A1 WO 2009056109A1 DE 2008001750 W DE2008001750 W DE 2008001750W WO 2009056109 A1 WO2009056109 A1 WO 2009056109A1
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WO
WIPO (PCT)
Prior art keywords
layer
polycarbonate
intermediate layer
polymer layer
polymer
Prior art date
Application number
PCT/DE2008/001750
Other languages
German (de)
English (en)
Inventor
André LEOPOLD
Oliver Muth
Michael Knebel
Rainer Seidel
Jens Ehreke
Manfred Paeschke
Heinz Pudleiner
Cengiz Yesildag
Klaus Meyer
Original Assignee
Bundesdruckerei Gmbh
Bayer Material Science Ag
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to PL08843351T priority Critical patent/PL2205436T3/pl
Application filed by Bundesdruckerei Gmbh, Bayer Material Science Ag filed Critical Bundesdruckerei Gmbh
Priority to RU2010121979/05A priority patent/RU2492057C2/ru
Priority to KR1020107007480A priority patent/KR101509838B1/ko
Priority to BRPI0818280-9A priority patent/BRPI0818280B1/pt
Priority to CN200880113954.6A priority patent/CN101842235B/zh
Priority to AT08843351T priority patent/ATE506182T1/de
Priority to JP2010530270A priority patent/JP5754025B2/ja
Priority to CA2703182A priority patent/CA2703182C/fr
Priority to EP20080843351 priority patent/EP2205436B1/fr
Priority to US12/740,787 priority patent/US20100291392A1/en
Priority to DE200850003312 priority patent/DE502008003312D1/de
Publication of WO2009056109A1 publication Critical patent/WO2009056109A1/fr
Priority to US15/610,768 priority patent/US10723109B2/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/05—Interconnection of layers the layers not being connected over the whole surface, e.g. discontinuous connection or patterned connection
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/75—Printability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2425/00—Cards, e.g. identity cards, credit cards
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2554/00—Paper of special types, e.g. banknotes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31507—Of polycarbonate

Definitions

  • the invention relates to a method for producing a composite having at least a first polymer layer and a second polymer layer each of a polycarbonate polymer based on bisphenol A, wherein an intermediate layer is arranged between the polymer layers, with the following process steps: the intermediate layer is at least in a partial region attached to the first polymer layer, then the second polymer layer is placed on the first polymer layer or the intermediate layer, and the first
  • Polymer layer and the second polymer layer are laminated together under pressure, at an elevated temperature and for a defined period of time.
  • the invention furthermore relates to a composite obtainable in this manner, to the use of the method for producing a security and / or value document, and to a security and / or value document that can be produced in this way.
  • Plastic cards are typically made by lamination of films formed as polymer layers. These are pressurized at a temperature above the softening point (glass point) of the Polymer layers is formed, an intimate bond between the polymer layers produced by the moving over the glass point polymer chains mix with each other and ideally an inseparable, monolithic composite of the polymer layers is obtained.
  • polymer layers may be partially provided with additional features, e.g. pigmentations are included to optimize blackening levels in laser engraving.
  • Additional elements are generally provided between the polymer layers; in particular, an intermediate layer, for example printed layer in the embodiment as security printing elements, such as guilloches, microfilm, etc., or special colors such as OVI ink, may be present on one of the polymer layers and in the finished bond between the polymer layers. like. be furnished.
  • an intermediate layer can also be, for example, a film with diffractive elements as a security feature.
  • Such an intermediate layer may only cover or be subject to a part of the underlying and / or overlying polymer layer, but may also be stacked with it congruently.
  • the intermediate layer can interfere with the abovementioned process of lamination, in particular if the intermediate layer is incompatible with the polymer layers to be joined. This incompatibility may be that the interlayer hinders the process of mixing the softened polymer layers as a release layer.
  • the weak point is thus at the interface between the printing layer and the applied and laminated second polymer layer. This can be particularly critical for full-surface imprints on the first polymer layer.
  • the invention is therefore based on the technical problem of a method for laminating a with Polycarbonate polymer layers not or only reduced to specify compatible intermediate layer between just such polycarbonate polymer layers, which results in a composite that ensures better security against delamination and consequently a very high integrity and durability of the composite produced.
  • the invention teaches a method for producing a composite with at least a first polymer layer and a second polymer layer, each consisting of a polycarbonate polymer based on bisphenol A, wherein between the first
  • an intermediate layer is arranged, with the following process steps: a) on at least a portion of the first polymer layer, the intermediate layer is applied, b) optionally, the intermediate layer is dried, c) the first polymer layer is on the side on which the Intermediate layer is arranged, at least partially coated with a liquid preparation containing a solvent or a solvent mixture and a polycarbonate derivative based on a gem disubstituted Dihydroxydiphenylcycloalkans coated, wherein the preparation covers the intermediate layer, preferably completely, d) optionally followed by step c) a drying process step, e) subsequently to stage c) or stage d), the second polymer layer is applied to the first polymer layer, the Covering the intermediate layer, laying it on, f) the first polymer layer and the second polymer layer are laminated together under pressure, at a temperature of 120 ° C. to 230 ° C. and for a defined period of time.
  • the invention is based firstly on the finding that polycarbonate derivatives used according to the invention are highly compatible with polycarbonate materials for films, in particular with polycarbonates based on bisphenol A, such as, for example, Makrofol® films.
  • the high compatibility is evident in the fact that the layer introduced according to the invention with a polycarbonate derivative adds the polycarbonate materials of the films into a monolithic composite. A layer boundary between the materials can no longer be detected optically after lamination.
  • a further advantage of the invention is that the liquid preparations used in accordance with the invention, in particular solutions, can be applied by printing technology and therefore have very high densities within the framework of the well-known printing processes (for example gravure, gravure, planographic and planographic printing but also ink jet printing) can be applied.
  • Commercially available adhesive systems eg based on epoxides could theoretically also be printed, but would discolor during lambing or lose their adhesive properties.
  • the intermediate layer can be, for example, a printing layer, in particular with a security printing element and / or a printed photographic representation, a photographic emulsion, and / or a film, in particular a diffractive security film. All intermediate layers known to the expert in the field of security and / or value documents come into consideration. It should be noted in this connection that the term intermediate layer also includes, of course, a plurality of adjacent small elements, such as the halftone dots of a printing layer.
  • the intermediate layer can be set up completely flat on the first polymer layer. But it is also possible that the intermediate layer is arranged only in a partial region of the surface of the first polymer layer. Likewise, the preparation can be applied completely flat on the first polymer layer provided with the intermediate layer, or only partially, but it is essential that the intermediate layer is completely covered.
  • the pressure m stage f) is typically in the range from 1 bar to 10 bar, in particular in the range from 3 bar to 7 bar.
  • the temperature in stage f) is preferably in the range 140 ° C. to 200 ° C., in particular in the range of 150 ° 0C to 180 0 C.
  • the duration of step e) may range from 0.5 s to 120 s, in particular 5 s s, and 60 lie, but is not relevant to the invention.
  • step d) at a temperature in the range 20 0 C to 120 0 C, in particular 60 0 C to 120 0 C, preferably 80 0 C to 110 0 C, for a period of at least 1 min., Preferably 5 mm. up to 600 mm., In particular 10 mm. to 120 mm., to be dried.
  • the intermediate layer is, for example, a printing layer, with the use of optional step b)
  • appropriate temperatures and / or durations can be used, but the temperature is instead less than 60 ° C., for example 20 ° C. to 60 ° C., and Duration may alternatively be less than 1 minute, for example 1 second to 60 seconds.
  • the layer thickness (m) c) produced (before or after drying) is, for example, in the range from 0.1 ⁇ m to 30 ⁇ m, preferably from 1 ⁇ m to 10 ⁇ m, in particular from 2 ⁇ m to 5 ⁇ m.
  • the polymer layers used can have a thickness in the range from 20 .mu.m to 1000 .mu.m, in particular from 50 .mu.m to 300 .mu.m.
  • the intermediate layer may have a thickness of 0.1 ⁇ m to 1000 ⁇ m, in particular from 1 ⁇ m to 50 ⁇ m.
  • print layers will typically have a layer thickness in the range of 1 .mu.m to 30 .mu.m.
  • photographic emulsions and / or other films, such as diffractive security films will have layer thicknesses in the range of 5 ⁇ m to 1000 ⁇ m, in particular 10 ⁇ m to 100 ⁇ m.
  • the polycarbonate derivative has a weight average molecular weight of at least 10,000, preferably from 20,000 to 300,000.
  • polycarbonate derivative may contain functional carbonate structural units of the formula (I),
  • R 1 and R 2 independently of one another, are hydrogen, halogen, preferably chlorine or bromine, C 1 -C 8 -alkyl, C 5 -C 6 - Cycloalkyl, C ⁇ -Cio-aryl, preferably phenyl, and Ci-Ci 2 - aralkyl, preferably phenyl-Ci-C 4 alkyl, in particular benzyl;
  • m is an integer from 4 to 7, preferably 4 or 5;
  • R 3 and R 4 are individually selectable for each X, independently of one another hydrogen or C 1 -C 6 -alkyl;
  • X is carbon and n is an integer large 20, with the proviso that on at least one atom X, R 3 and R 4 are simultaneously alkyl.
  • X, R 3 and R 4 are simultaneously alkyl at 1 to 2 atoms, in particular only at one atom.
  • R 3 and R 4 may be in particular methyl.
  • the X atoms alpha to the diphenyl-substituted C atom (Cl) may not be dialkyl-substituted.
  • the X atoms in beta position to Cl can be disubstituted with alkyl.
  • m 4 or 5.
  • the polycarbonate derivative can be prepared, for example, on the basis of monomers, such as 4,4 ' - (3,3,5-methylcyclohexan-1,1-diyl) -diphenol. 4,4 ' - (3,3 dimethylcyclohexane-1,1-diyl) diphenol, or 4,4 '- (2,4,4-trimethylcyclopentane-1,1-diyl) diphenol.
  • Em inventive polycarbonate derivative can be prepared, for example, according to the document DE 38 32 396.6 from diphenols of the formula (Ia), the disclosure of which is hereby incorporated in full extent m the disclosure content of this description.
  • diphenols of the formula (Ia) may also be mixed with other diphenols, for example those of the formula (Ib)
  • thermoplastic aromatic polycarbonate derivatives
  • Suitable other diphenols of the formula (Ib) are those in which Z is an aromatic radical having 6 to 30 C atoms, which may contain one or more aromatic nuclei, may be substituted, and aliphatic radicals or cycloaliphatic radicals other than those of the formula (II) Ia) or heteroatoms may contain as bridge members.
  • diphenols of the formula (Ib) are: hydroquinone, resorcinol, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) ethers.
  • Preferred other diphenols are, for example: 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1, 1-bis ( 4-hydroxyphenyl) -cyclohexane, alpha, alpha -bis (4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis (3-methyl) chloro-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, 2,2-BxS- (3,5-dimethyl-4-hydroxyphenyl) -propane, bis (3, 5-dimethyl-4-hydroxyphenyl) sulfone, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1, 1-bis (3,5-dimethyl-4-hydroxyphenyl) -cyclohex
  • diphenols of the formula (Ib) are, for example: 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3, S-dimethyl-4-hydroxyphenyl) -propane, 2,2-bis - (3,5-dichloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dibromo-4-hydroxyphenyl) -propane and 1,1-bis- (4-hydroxyphenyl) -cyclohexane.
  • 2, 2-bis (4-hydroxyphenyl) propane is preferred.
  • the other diphenols can be used both individually and in a mixture.
  • the molar ratio of diphenols of the formula (Ia) to the optionally used other diphenols of the formula (Ib) should be between 100 mol% (Ia) to 0 mol% (Ib) and 2 mol% (Ia) to 98 mol -% (Ib), preferably between 100 mol% (Ia) to 0 mol% (Ib) and 10 mol% (Ia) to 90 mol% (Ib) and especially between 100 mol% (Ia) to 0 mol% (Ib) and 30 mol% (Ia) to 70 mol% (Ib).
  • the high molecular weight polycarbonate derivatives of the diphenols of the formula (Ia), optionally in combination with other diphenols, can according to the known
  • Polycarbonate production process can be produced.
  • the various diphenols can be linked together both statistically and in blocks.
  • the polycarbonate derivatives used according to the invention can be branched in a manner known per se. If the branching is desired, it is possible, by known means, to bind three or more trifunctional groups by condensing small quantities, preferably amounts between 0.05 and 2.0 mol% (based on the diphenols used) Compounds, especially those having three or more than three phenolic hydroxyl groups, can be achieved.
  • Some branching agents having three or more than three phenolic hydroxyl groups are: phloroglucinol, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) -heptene-2, 4, 6-dir ⁇ -ethyl-2,4,6 tri- (4-hydroxyphenyl) heptane, 1,3,5-tri (4-hydroxyphenyl) benzene, 1,1,1-tri (4-hydroxyphenyl) ethane, tri- (4-hydroxyphenyl) - phenylmethane, 2,2-bis- [4,4-bis (4-hydroxyphenyl) cyclohexyl] -propane, 2,4-bis (4-hydroxyphenyl-isopropyl) -phenol, 2,6-iso- (2 -hydroxy-5-methyl-benzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) -propane, hexa- [4-hydroxyphenyl)
  • trifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.
  • Suitable compounds are e.g. Phenol, tert. Butylphenols or other alkyl-substituted phenols.
  • phenols of the formula (Ic) are suitable
  • R is a branched Cs and / or Cg alkyl radical.
  • the chain terminators are generally used in amounts of 0.5 to 10, preferably 1.5 to 8 mol%, based on diphenols used.
  • the polycarbonate derivatives may preferably be prepared in a manner known per se according to the phase boundary behavior (compare H. Schnell "Chemistry and Physics of Polycarbonates", Polymer Reviews, Vol. IX, page 33 et seq., Interscience Publ.
  • the diphenols of the formula (Ia) are dissolved in an aqueous alkaline phase.
  • mixtures of diphenols of the formula (Ia) and the other diphenols, for example those of the formula (Ib), are used.
  • chain terminators of, for example, the formula (Ic) can be added.
  • organic phase reacted with phosgene by the method of interfacial condensation.
  • the reaction temperature is between 0 0 C and 40 0 C.
  • the optionally used branching agents can either be initially charged with the diphenols in the aqueous alkaline phase or added to the organic solvent dissolved before phosgenation.
  • diphenols of the formula (Ia) and, if appropriate, other diphenols (Ib) it is also possible to use their mono- and / or bis-chlorocarbonic esters, these being added dissolved in organic solvents.
  • the amount of chain terminators and of branching agents then depends on the molar amount of diphenolate radicals corresponding to formula (Ia) and optionally formula (Ib); When using chlorocarbonic acid esters, the amount of phosgene can be reduced accordingly in a known manner.
  • Suitable organic solvents for the chain terminators and optionally for the branching agents and the chlorocarbonic acid esters are, for example, methylene chloride, chlorobenzene, in particular mixtures of methylene chloride and chlorobenzene. If necessary, the used
  • Chain terminators and branching agents are dissolved in the same solvent.
  • the organic phase used for the phase boundary polycondensation is, for example, methylene chloride,
  • Chlorobenzene and mixtures of methylene chloride and chlorobenzene Chlorobenzene and mixtures of methylene chloride and chlorobenzene.
  • the aqueous alkaline phase used is, for example, NaOH solution.
  • the preparation of the polycarbonate derivatives by the phase boundary method can in the usual way Catalysts such as tertiary amines, in particular tertiary aliphatic amines such as tributylamine or triethylamine are catalysed; the catalysts can m quantities of 0.05 to 10 mol%, based on moles of diphenols used, are used. The catalysts can be added before the beginning of the phosgenation or during or after the phosgenation.
  • the polycarbonate derivatives can be prepared by the known method in the homogeneous phase, the so-called “Pyridm Kunststoffmaschinen" as well as by the known melt transesterification process using, for example, diphenyl carbonate instead of phosgene.
  • the polycarbonate derivatives may be linear or branched, they are homopolycarbonates or copolycarbonates based on the diphenols of the formula (Ia).
  • the polycarbonate properties can be varied in a favorable manner.
  • the diphenols of the formula (Ia) are present in amounts of from 100 mol% to 2 mol%, preferably in amounts of from 100 mol% to 10 mol% and in particular in amounts of from 100 mol% to 30 mol% %, based on the total amount of 100 mol% of Diphenolem reel contained in Polycarbonatede ⁇ vaten.
  • a particularly advantageous embodiment of the invention is characterized in that the polycarbonate derivative a copolymer comprising, in particular consisting of, monomer units M1 based on the formula (Ib), in particular bisphenol A, and monomer units M2 based on the geminally disubstituted dihydroxydiphenylcycloalkane, preferably the
  • the glass transition temperature can be increased after a first heating cycle of T 9 below 150 0 C in a second heating cycle, which can significantly increase the stability of the resulting composite.
  • liquid preparation comprising: A) 1 to 30% by weight, preferably 10 to 25% by weight, in particular 15 to 20% by weight, of a polycarbonate derivative used according to the invention, and B) 70 to 99% by weight. -%, Preferably 75 to 90 wt .-%, in particular 80 to 85 wt .-%, of an organic solvent or solvent mixture.
  • the organic solvents used are preferably halogen-free organic solvents.
  • Particularly suitable are aliphatic, cycloaliphatic, aromatic hydrocarbons, such as mesitylene, 1,2,4-t-methylbenzene, cumene and solvent naphtha, toluene, xylene; (organic) esters such as methyl acetate, ethyl acetate, butyl acetate, methoxypropyl acetate, ethyl 3-ethoxypropionate.
  • mesitylene 1, 2, 4-trimethylbenzene, cumene and solvent naphtha
  • toluene xylene
  • methyl acetate Essigsa ⁇ reethylester
  • methoxypropyl acetate methoxypropyl acetate.
  • Ethyl 3-ethoxypropionate very particular preference is given to mesitylene (1,3,5-trimethylbenzene), 1,2,4-trimethylbenzene, cumene (2-phenylpropane), solvent naptha and ethyl 3-ethoxypropionate.
  • a suitable solvent mixture comprises, for example, A) 0 to 10% by weight, preferably 1 to 5% by weight, in particular 2 to 3% by weight, mesitylene, B) 10 to 50% by weight, preferably 25 to 50% by weight %, in particular 30 to 40% by weight, of 1-methoxy-2-propanol acetate, C) 0 to 20% by weight, preferably 1 to 20% by weight, in particular 7 to 15% by weight, 1 , 2, 4-trimethylbenzene, D) 10 to 50 wt .-%, preferably 25 to 50 wt .-%, in particular 30 to 40 wt .-%, ethyl 3-ethoxypropionate, E) 0 to 10 wt .-% , preferably 0.01 to 2 wt .-%, in particular 0.05 to 0.5 wt .-%, cumene, and 0 to 80 wt .-%, preferably 1 to 40 wt .-%, in particular 15 to 25 wt .
  • the first polycarbonate layer and the second polycarbonate layer have a glass transition temperature T g of more than 145 0 C, in particular more than 147 ° C, on.
  • the invention further relates to a composite obtainable by a method according to the invention.
  • a composite may comprise a first polycarbonate layer, a second polycarbonate layer, an intermediate layer disposed between the first polycarbonate layer and the second polycarbonate layer, and an intermediate layer with the second polycarbonate layer having connecting preparation layer containing a polycarbonate derivative based on a geminal disubstituted Dihydroxydiphenylcycloal kans, wherein the polycarbonate layers and the intermediate layer may each be materially interconnected.
  • the invention furthermore relates to the use of a method according to the invention for the production of a security and / or value document, optionally simultaneously with, or before or after the production of the composite, the first polycarbonate layer and / or the second polycarbonate layer with at least one further layer, for example one Support layer, directly or indirectly connected.
  • security and / or value documents are: identity cards, passports, ID cards, access control cards, visas, tax stamps, tickets, driver's licenses,
  • Such security and / or valuable documents typically have at least one substrate, one print layer and optionally a transparent cover layer.
  • Substrate and cover layer may in turn consist of a plurality of layers.
  • a substrate is a support structure to which the
  • Suitable materials for a substrate are all suitable materials based on paper and / or (organic) polymers in question.
  • Such a security and / or value document comprises a composite according to the invention within the overall layer composite.
  • At least one (possibly additional) print layer which may be attached between the two polymer layers, on an outer surface of the composite or on a further layer connected to the composite, may also be arranged in the composite according to the invention
  • FIG. 1 Layer thickness measurements on a printing-technologically produced layer with the preparation used according to the invention, after a single print (FIG. 1a) and after printing twice
  • Figure 2 process flow of the production of a
  • Example 1.1 Preparation of a first polycarbonate derivative 205.7 g (0.90 mol) of bisphenol A (2,2-bis (4-hydroxyphenyl) propane, 30.7 g (0.10 mol) of 1,1-bis (4-hydroxyphenyl) -3 3, 5-methylmethylcyclohexane, 336.6 g (6 moles) of KOH and 2700 g of water are dissolved in an inert gas atmosphere while stirring, then a solution of 1.88 g of phenol in 2500 ml of methylene chloride is added stirred solution was added 13 to 14 and 21 to 25 0 C, 198 g (2 moles) phosgene in pH. Thereafter, 1 ml Ethylpiperidm is added and a further 45 min. stirring. the bisphenolate aqueous phase is separated, the organic phase after acidification with phosphoric acid washed neutral with water and freed from the solvent.
  • bisphenol A 2,2-bis (4-hydroxyphenyl) propane
  • the polycarbonate derivative showed a relative solution viscosity of 1.255.
  • the glass transition temperature was determined to be 157 ° C. (DSC).
  • the polycarbonate derivative showed a relative solution viscosity of 1.263.
  • the glass transition temperature was determined to be 167 ° C. (DSC).
  • the polycarbonate derivative showed a relative solution viscosity of 1.263.
  • the glass transition temperature was determined to be 183 ° C. (DSC).
  • the polycarbonate derivative showed a relative solution viscosity of 1.251.
  • the glass transition temperature was determined to be 204 ° C. (DSC).
  • Example 1.5 Making a fifth
  • Example 2 As in Example 1, a mixture of 44.2 g (0.19 mol) of bisphenol A and 250.4 g (0.81 mol) of 1,1'-bis (4: 1) hydroxyphenyl) -3, 3, 5-tnmethylcyclohexan reacted to polycarbonate.
  • the polycarbonate derivative showed a relative solution viscosity of 1.248.
  • the glass transition temperature was determined to be 216 ° C. (DSC).
  • a first liquid preparation was prepared from 17.5 parts by weight of the polycarbonate derivative of Example 1.3 and 82.5 parts by weight of a Lsgm. Mixture prepared according to Table I.
  • the formulations of Table II were knife-coated on glass plates for the purpose of determining the softening temperatures, so that dry layer thicknesses of 5 ⁇ m were obtained.
  • the coatings were dried for 1 hour at 100 0 C in a vacuum oven. Subsequently, the dried films were peeled from the glass plate and examined by differential scanning calometry (DSC).
  • the film of Example 1.3 after drying during the first heating shows a softening temperature of 128.54 0 C. Only at
  • a polycarbonate film 1 Makrofol® 6-2 (thickness about 100 ⁇ m) is coated with an intermediate layer 3, in the exemplary embodiment a print layer 3 (FIG. 2a), for example by means of offset or screen printing.
  • a printing layer can be seen from a screened printing, while on the right side a printing layer 3 is shown from a full-surface printing. If necessary, the printing layer 3 is first dried. Then the one with the
  • Print layer 3 provided side of the polycarbonate film 1, for example by screen printing with a preparation layer 4 of a composition of Example 2, for example based on the polycarbonate derivative according to Example 1.3 and the
  • Solvent mixture according to Table I provided ( Figure 2b). This can be either full-flattened, or, as shown, only partially, covering the areas of the print layer 3. Screen printing is done once or twice. Then it is dried under air at 100 0 C for 60 mm. This results in a layer thickness of about 2.2 ⁇ m or 3.3 ⁇ m of the dried polycarbonate denvate (FIG. 2b).
  • the composite turned out to be a monolithic block.

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  • Laminated Bodies (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un procédé de production d'un composite comportant au moins une première couche de polymère et une deuxième couche de polymère, chacune constituée d'un polycarbonate à base de bisphénol A, une couche intermédiaire étant disposée entre la première et la deuxième couche de polymère. Ce procédé comprend les étapes suivantes : a) la couche intermédiaire est appliquée sur au moins une partie de la première couche de polymère; b) la couche intermédiaire est séchée optionnellement; c) sur le côté sur lequel la couche intermédiaire a été appliquée, la première couche de polymère est enduite d'une préparation liquide contenant un solvant ou un mélange de solvant et un dérivé de polycarbonate à base d'un dihydroxydiphénylcycloalcane à double substitution géminée, cette préparation recouvrant la couche intermédiaire; d) une étape de séchage est mise en oeuvre optionnellement à l'issue de l'étape c); e) à l'issue de l'étape c) ou de l'étape d), la deuxième couche de polymère est appliquée sur la première couche de polymère de manière à recouvrir la couche intermédiaire; f) la première et la deuxième couche de polymère sont stratifiées l'une sur l'autre par pression à une température comprise entre 120 °C et 230 °C pendant une durée définie.
PCT/DE2008/001750 2007-10-31 2008-10-29 Procédé de production d'un composite stratifié à base de polycarbonate WO2009056109A1 (fr)

Priority Applications (12)

Application Number Priority Date Filing Date Title
AT08843351T ATE506182T1 (de) 2007-10-31 2008-10-29 Verfahren zur herstellung eines polycarbonat- schichtverbundes
RU2010121979/05A RU2492057C2 (ru) 2007-10-31 2008-10-29 Способ изготовления поликарбонатного слоистого композита
KR1020107007480A KR101509838B1 (ko) 2007-10-31 2008-10-29 폴리카보네이트 층상 복합재의 제조방법
BRPI0818280-9A BRPI0818280B1 (pt) 2007-10-31 2008-10-29 Compósito, seu processo de produção e seu uso, e documento de segurança e/ou de valor
CN200880113954.6A CN101842235B (zh) 2007-10-31 2008-10-29 用于制造聚碳酸酯多层复合物的方法
PL08843351T PL2205436T3 (pl) 2007-10-31 2008-10-29 Sposób produkcji poliwęglanowego kompozytu warstwowego
JP2010530270A JP5754025B2 (ja) 2007-10-31 2008-10-29 ポリカーボネート多層ポリマー構造体を作製する方法
US12/740,787 US20100291392A1 (en) 2007-10-31 2008-10-29 Method for producing a polycarbonate layered composite
EP20080843351 EP2205436B1 (fr) 2007-10-31 2008-10-29 Procédé de production d'un composite stratifié à base de polycarbonate
CA2703182A CA2703182C (fr) 2007-10-31 2008-10-29 Methode pour produire une structure multicouche en polycarbonate
DE200850003312 DE502008003312D1 (de) 2007-10-31 2008-10-29 Verfahren zur herstellung eines polycarbonat-schichtverbundes
US15/610,768 US10723109B2 (en) 2007-10-31 2017-06-01 Method for producing a polycarbonate layered composite

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007052949.1 2007-10-31
DE200710052949 DE102007052949A1 (de) 2007-10-31 2007-10-31 Verfahren zur Herstellung eines Polycarbonat-Schichtverbundes

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US12/740,787 A-371-Of-International US20100291392A1 (en) 2007-10-31 2008-10-29 Method for producing a polycarbonate layered composite
US15/610,768 Continuation US10723109B2 (en) 2007-10-31 2017-06-01 Method for producing a polycarbonate layered composite

Publications (1)

Publication Number Publication Date
WO2009056109A1 true WO2009056109A1 (fr) 2009-05-07

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE2008/001750 WO2009056109A1 (fr) 2007-10-31 2008-10-29 Procédé de production d'un composite stratifié à base de polycarbonate

Country Status (14)

Country Link
US (2) US20100291392A1 (fr)
EP (1) EP2205436B1 (fr)
JP (1) JP5754025B2 (fr)
KR (1) KR101509838B1 (fr)
CN (1) CN101842235B (fr)
AT (1) ATE506182T1 (fr)
BR (1) BRPI0818280B1 (fr)
CA (1) CA2703182C (fr)
DE (2) DE102007052949A1 (fr)
ES (1) ES2362468T3 (fr)
PL (1) PL2205436T3 (fr)
RU (1) RU2492057C2 (fr)
TW (1) TWI451972B (fr)
WO (1) WO2009056109A1 (fr)

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DE102010041975A1 (de) * 2010-10-05 2012-04-05 Bundesdruckerei Gmbh Verfahren zum Erfassen eines Wert- und/oder Sicherheitsdokuments
DE102012203270A1 (de) * 2012-03-01 2013-09-05 Bundesdruckerei Gmbh Dokument und Verfahren zum Herstellen des Dokuments
DE102012216126A1 (de) 2012-09-12 2014-03-13 Bundesdruckerei Gmbh Verfahren zum flächigen Verbinden von Polymerfolien mittels eines Laminierverfahrens, Polymerfolienverbund, dessen Verwendung sowie daraus gebildetes Wert- und/oder Sicherheitsdokument
EP3074700A4 (fr) 2013-11-29 2018-05-16 Kim, No Eul Chaudière à eau chaude en plastique
EP4279290A1 (fr) * 2017-02-16 2023-11-22 Dai Nippon Printing Co., Ltd. Page d'informations
KR102021377B1 (ko) 2018-01-29 2019-09-16 공주대학교 산학협력단 탄소계 필러 함유 전기전도성 폴리카보네이트 나노복합소재의 제조방법 및 그에 의해 제조된 전기전도성 폴리카보네이트 나노복합소재
DE102020129323A1 (de) 2020-11-06 2022-05-12 Bundesdruckerei Gmbh Datenträger für ein Sicherheits- oder Wertdokument mit magnetischem Sicherheitsmerkmal

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Also Published As

Publication number Publication date
ATE506182T1 (de) 2011-05-15
DE502008003312D1 (de) 2011-06-01
BRPI0818280A2 (pt) 2015-04-14
CA2703182C (fr) 2016-08-30
RU2492057C2 (ru) 2013-09-10
TWI451972B (zh) 2014-09-11
DE102007052949A1 (de) 2009-05-07
EP2205436B1 (fr) 2011-04-20
BRPI0818280B1 (pt) 2019-06-18
TW200946342A (en) 2009-11-16
KR20100092426A (ko) 2010-08-20
KR101509838B1 (ko) 2015-04-08
JP5754025B2 (ja) 2015-07-22
ES2362468T3 (es) 2011-07-06
CN101842235A (zh) 2010-09-22
US20170266936A1 (en) 2017-09-21
RU2010121979A (ru) 2011-12-10
JP2011502036A (ja) 2011-01-20
US20100291392A1 (en) 2010-11-18
US10723109B2 (en) 2020-07-28
PL2205436T3 (pl) 2011-09-30
CA2703182A1 (fr) 2009-05-07
EP2205436A1 (fr) 2010-07-14
CN101842235B (zh) 2015-09-23

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